EP0484368B1 - Procede de fermeture d'une extremite du boitier d'une cellule a sodium/soufre et cellule a sodium/soufre produite par ce procede - Google Patents
Procede de fermeture d'une extremite du boitier d'une cellule a sodium/soufre et cellule a sodium/soufre produite par ce procede Download PDFInfo
- Publication number
- EP0484368B1 EP0484368B1 EP90910813A EP90910813A EP0484368B1 EP 0484368 B1 EP0484368 B1 EP 0484368B1 EP 90910813 A EP90910813 A EP 90910813A EP 90910813 A EP90910813 A EP 90910813A EP 0484368 B1 EP0484368 B1 EP 0484368B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- case
- closure member
- sodium
- annular flange
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/147—Lids or covers
- H01M50/148—Lids or covers characterised by their shape
- H01M50/1535—Lids or covers characterised by their shape adapted for specific cells, e.g. electrochemical cells operating at high temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49114—Electric battery cell making including adhesively bonding
Definitions
- This invention relates to a sodium/sulphur cell, and in particular to a method of closing the case of a sodium/sulphur cell.
- US-A-3294591 Jordan - assignee Gulton discloses a sealed battery construction for use in rechargeable nickel-cadmium and sulphur-cadmium batteries.
- the upper end of a casing body is turned outwardly to form a horizontal shoulder on which the correspondingly shaped perimeter of a metal member is connected and sealed as by welding.
- Both the casing body and the metal member may be made of nickel-plated steel.
- US-A-4048393 (Heintz et al - assignee Ford) discloses alkali metal battery structures.
- a closed metal housing made from a material such as stainless steel, has an upper dome portion and a flange which extends inwardly of the dome portion.
- the flange 14 is brazed to a first ceramic member.
- the first ceramic member is, in turn, brazed to an inwardly extending flange of a second metal housing to form the structure.
- the ceramic member has an outwardly extending flange which is bonded to a surface of a ceramic container to form the structure.
- GB-A-2083686 (B.B.C.) discloses an electrochemical storage cell.
- the metal casing has an outwardly directed flange.
- the surface of the outwardly directed flange is covered by a protected layer preferably made of a thermocompression material.
- the flange acts as a bearing surface for a solid electrolyte formed of a beta aluminium oxide tube and an annular insulating member.
- the protective layer may be joined to the edge of the beta aluminium oxide tube and the insulating member with the aid of the thermocompression process.
- JP-A-63-62165 discloses a sodium/sulphur battery.
- the battery includes a negative vessel and a positive electrode vessel separated by a solid electrolyte vessel.
- a positive electrode supplementary vessel is joined to the positive electrode vessel at an end face and sealed.
- a solid electrolyte - generally beta alumina - separates two liquid electrodes, namely liquid sulphur and liquid sodium electrodes.
- FIG. 1 of the drawings is a perspective view of the cell with part broken away.
- the cell comprises a case 1 of, for example, steel in the form of a right circular cylinder and containing a solid electrolyte cup 2 of beta alumina, the cup 2 containing a sodium electrode 3, while a space between the case 1 and the cup 2 contains a sulphur electrode 4.
- the cell is maintained at a temperature of between 300°C and 400°C such that the sodium and sulphur electrodes 3 and 4 are in liquid form.
- the open end of the cup 2 is closed by an insulating disc 5 of alpha alumina, while the case 1 is closed by an annular sealing closure disc 6 of steel.
- the case 1 serves as a terminal for the sulphur electrode 4, while the sodium electrode 3 contains an elongate metal current collector 8 which extends axially of the case 1 out through the disc 5 where it is connected to a centre terminal disc 7 mounted on the disc 5, the necessary connections being made by welding.
- sulphur is essentially non-conducting a means of making an electrical connection between the case 1 and the cup 2 has to be provided, and this is generally achieved by forming the sulphur electrode 4 as a carbon fibre mat impregnated with sulphur.
- alpha alumina disc 5 With such a cell it is necessary for the alpha alumina disc 5 to seal the open end of the beta alumina cup 2 and this is generally effected by a glazing technique. It is also necessary for the disc 6 and the terminal disc 7 to be secured to the alpha alumina disc 5 to form seals, and since alpha alumina is both ionically and electronically insulating diffusion bonding is generally used.
- each of the case and the closure member is formed of a composite material consisting of a metal substrate and a deformable metal layer mechanically fixed to said substrate, said substrate being formed of a material which is harder than said deformable metal; and in that the method comprises the steps of forming an outwardly extending annular flange at the open end of the case and securing the closure member to the annular flange at interfacing surfaces thereof with the deformable metal layer being at said interfacing surfaces by solid phase bonding thereby to close the case.
- the annular flange and the part of the closure member secured thereto are bent to extend about the outside of the case with the free edges of the annular flange and the closure member directed away from the end of the case closed by the closure member.
- the case is kinked inwardly below the position of the free edges of the annular flange and the closure member such that the overall diameter of the cell is no more than the basic diameter of the case.
- the closure member can be secured to the annular flange by any one of a number of methods of solid phase bonding such as ultrasonic welding, high speed diffusion bonding (thermocompression) and cold welding.
- a sodium/sulphur cell including a case closed at one end by a closure member, characterised in that each of the case and the closure member is formed of a composite material consisting of a substrate and a deformable metal layer mechanically fixed to said substrate, said substrate being formed of a material which is harder than said deformable metal, said one end of said case being formed to include an outwardly extending annular flange and the closure member being secured to said annular flange at interfacing surfaces thereof with the deformable metal layer being at said interfacing surfaces by a solid phase bond.
- annular flange and the part of the closure member secured thereto are bent to extend about the outside of the case with the free edges of the annular flange and the closure member directed away from said one end of the case.
- the case is kinked inwardly below the position of the free edges of the annular flange and the closure member such that the overall diameter of the cell is no more than the basic diameter of the case.
- FIG 2 this illustrates the conventional way of securing the closure member 6 to the case 1 of the cell.
- the closure member 6 has an upstanding peripheral flange 9 which is secured inside the case 1 by electron beam welding, laser welding or TIG welding as discussed above.
- FIG 3 this illustrates the connection of a closure member 16 to a case 11 by the method of this invention.
- an outwardly extending annular flange 20 is formed at the open end of the case 11, and the closure member 16 is formed to extend over the flange 20 and is secured thereto by ultrasonic welding.
- the other parts of the sodium/sulphur cell of Figure 3 are similar to parts of the sodium/sulphur cell of Figures 1 and 2 and accordingly corresponding reference numerals are used for corresponding parts.
- Each of the case 11 and closure member 16 is formed of a composite material consisting of a steel substrate with a layer of a deformable metal, such as aluminium or an alumunium alloy, mechanically fixed to the substrate.
- the weld between the case 11 and the closure member 16 is formed on a diameter greater than the diameter of the case 11 and is of annular form. As can be seen in Figure 3, the weld is formed away from the part of the cell containing the electrode materials and so any damage or weakening of the composite material of the case 11 or closure member 16 caused by the welding process is not exacerbated by corrosive attack by the electrode materials.
- the weld or bond between the case 11 and the closure member 16 is a solid phase bond produced by a method of solid phase bonding such as diffusion bonding (thermocompression), ultrasonic welding or cold welding.
- a method of solid phase bonding such as diffusion bonding (thermocompression), ultrasonic welding or cold welding.
- An apparatus for ultrasonically welding together the flange 20 of the case 11 and the closure member 16 is shown in Figure 4. This apparatus is not part of the invention.
- the two members to be ultrasonically welded together, the workpiece, are shown at 21 as two components 21a, 21b.
- a frequency generator 22 which can produce an output of between 10 and 36 kHz is used to produce a high frequency output signal at the desired frequency.
- This signal is coupled to a piezoelectric crystal 24 which responds by delivering a small amount of movement at a similar frequency to the applies signal.
- the movement is transmitted to the workpiece 21 by means of a sonotrode 26.
- the annular sonotrode 26 is of the required size and made of hardened steel, titanium or some other suitable material and is shaped so that the ultrasonic movement (direction indicated by the arrow A) is amplified and then focused at the desired position.
- the ultrasonic movement is transmitted to the top component 21a by serrations 27 in the sonotrode 26.
- the serrations 27 in the surface of the sonotrode embed themselves into the material so transmitting ultrasonic movement to the top component 21a.
- the bottom component 21b is located on a support 28.
- the serrations (not shown) of the support 28 fix the bottom component 21b in position so that relative movement can take place between the top and bottom components 21a, 21b during welding.
- the present apparatus uses a lateral driven sonotrode so that the movement of the welding tip relative to the weld interface is non-torsional with only a translational ultrasonic movement being used to generate the weld.
- a sonotrode may be used as a continuous seam welder in which the welding tip is positioned adjacent the top component and the workpiece is rotated relative to the sonotrode.
- the top component 21a consists of the closure member 16 of the sodium/sulphur cell while the bottom component 21b consists of the annular flange 20 of the case 11. Because the closure member 16 is welded to the flange 20 of the case 11, the welding load can be applied as an axial pressure. As compared with the application of pressure radially, the application of pressure axially has the advantage of simplicity.
- the combination of the positon of the weld and the solid phase bond produced by the method according to the present invention enables the provision of a hermetic bond between the case and closure member of the sodium/sulphur cell.
- the flange 20 extends substantially perpendicularly to the wall of the case 11, it will be appreciated that it can otherwise extend at any other suitable angle in dependence on the welding tool to be used.
- the flange 20 and the part of the closure member 16 secured thereto can be bent to extend about the outside of the case 11 with the free edges of the flange 20 and the closure member 16 directed away from the end of the case 11 closed by the closure member 16, thereby to reduce the maximum overall diameter of the cell.
- the wall of the case 11 can be kinked inwardly, as shown at 31, in order that the maximum overall diameter of the cell is no more than the basic diameter of the case 11.
- the flange 20 of the case 11, the corresponding part of the closure member 16 and the kink 31 in the wall of the case 11 can be produced during formation of the case 11 and closure member 16 by methods known to those skilled in the art.
- closure member could be formed of a composite material in which the substrate was formed of a material such as aluminium with ceramic reinforcing fibres.
Claims (8)
- Procédé de fermeture d'une extrémité d'un boîtier d'une pile au sodium/soufre par fixation d'un élément de fermeture à une extrémité, caractérisé en ce que :
chacun du boîtier et de l'élément de fermeture est fait d'une matière composite constituée d'un substrat et d'une couche métallique déformable fixée mécaniquement audit substrat, le substrat étant fait d'une matière qui est plus dure que le métal déformable ;
et en ce que le procédé comprend les étapes de formation d'une collerette annulaire s'étendant vers l'extérieur au droit de ladite une extrémité du boîtier, et de fixation de l'élément de fermeture à la collerette annulaire, par une liaison autogène, au droit de leurs surfaces formant interface, la couche métallique déformable se trouvant au droit desdites surfaces formant interface, pour fermer ainsi le boîtier. - Procédé selon la revendication 1, comprenant en outre l'étape de pliage de la collerette annulaire et de la partie de l'élément de fermeture qui y est fixé de manière à s'étendre autour de l'extérieur du boîtier, les bords libres de la collerette annulaire et de l'élément de fermeture étant dirigés vers l'extérieur de ladite une extrémité du boîtier fermé par ledit élément de fermeture.
- Procédé selon la revendication 1 ou 2, comprenant en outre l'étape de formation du boîtier pour qu'il soit déformé vers l'intérieur au-dessous de la position des bords libres de la collerette annulaire et de l'élément de fermeture, de façon telle que le diamètre hors tout de la pile ne soit pas plus grand que le diamètre de base du boîtier.
- Procédé selon l'une quelconque des revendications précédentes, dans laquelle ladite liaison autogène est réalisée par soudage aux ultrasons.
- Pile au sodium/soufre comprenant un boîtier fermé à une extrémité par un élément de fermeture, caractérisé en ce que chacun du boîtier et de l'élément de fermeture est fait d'une matière composite constituée d'un substrat et d'une couche métallique déformable fixée mécaniquement audit substrat, le substrat étant fait d'une matière qui est plus dure que le métal déformable, une extrémité du boîtier étant formée de manière à comprendre une collerette annulaire s'étendant vers l'extérieur et l'élément de fermeture étant fixé à ladite collerette annulaire, par une liaison autogène, au droit de leurs surfaces formant interface, la couche métallique déformable se trouvant au droit desdites surfaces formant interface.
- Pile au sodium/soufre selon la revendication 5, dans laquelle ledit substrat est fait d'un métal.
- Pile au sodium/soufre selon la revendication 5 ou 6, dans laquelle ladite collerette annulaire et de la partie de l'élément de fermeture qui y est fixé sont pliés de manière à s'étendre autour de l'extérieur du boîtier, les bords libres de la collerette annulaire et de l'élément de fermeture étant dirigés vers l'extérieur de ladite une extrémité du boîtier fermé par ledit élément de fermeture.
- Pile au sodium/soufre selon l'une quelconque des revendications 5 à 7, dans laquelle le boîtier est déformé vers l'intérieur au-dessous de la position des bords libres de la collerette annulaire et de l'élément de fermeture, de façon telle que le diamètre hors tout de la pile ne soit pas plus grand que le diamètre de base du boîtier.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8917022 | 1989-07-25 | ||
GB898917022A GB8917022D0 (en) | 1989-07-25 | 1989-07-25 | Sodium/sulphur cell |
PCT/GB1990/001136 WO1991001571A1 (fr) | 1989-07-25 | 1990-07-24 | Procede de fermeture d'une extremite du boitier d'une cellule a sodium/soufre et cellule a sodium/soufre produite par ce procede |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0484368A1 EP0484368A1 (fr) | 1992-05-13 |
EP0484368B1 true EP0484368B1 (fr) | 1995-04-05 |
Family
ID=10660611
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90910813A Expired - Lifetime EP0484368B1 (fr) | 1989-07-25 | 1990-07-24 | Procede de fermeture d'une extremite du boitier d'une cellule a sodium/soufre et cellule a sodium/soufre produite par ce procede |
Country Status (11)
Country | Link |
---|---|
US (1) | US5279625A (fr) |
EP (1) | EP0484368B1 (fr) |
JP (1) | JPH04507030A (fr) |
CN (1) | CN1049753A (fr) |
AT (1) | ATE120886T1 (fr) |
CA (1) | CA2063802A1 (fr) |
DD (1) | DD300890A5 (fr) |
DE (1) | DE69018468T2 (fr) |
GB (1) | GB8917022D0 (fr) |
WO (1) | WO1991001571A1 (fr) |
ZA (1) | ZA905639B (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9020828D0 (en) * | 1990-09-25 | 1990-11-07 | Chloride Silent Power Ltd | A sodium/sulphur cell and a method of closing one end of the case of a sodium/sulphur cell |
GB2265048A (en) * | 1990-09-25 | 1993-09-15 | Chloride Silent Power Ltd | A sodium electrode energy conversion device and a method of closing the case of a sodium electrode energy conversion device |
GB9111982D0 (en) * | 1991-06-04 | 1991-07-24 | Chloride Silent Power Ltd | An alkali metal energy conversion cell |
JP3316338B2 (ja) * | 1995-05-30 | 2002-08-19 | 三洋電機株式会社 | 角型電池 |
US6265101B1 (en) * | 1998-08-21 | 2001-07-24 | Eveready Battery Company, Inc. | Battery constructions having increased internal volume for active components |
US6410186B1 (en) * | 1998-08-21 | 2002-06-25 | Eveready Battery Company, Inc. | Battery construction having double seam cover closure |
JP2000216596A (ja) * | 1999-01-25 | 2000-08-04 | Sanyo Electric Co Ltd | 電子部品自動装着装置 |
US8168350B1 (en) | 2002-07-02 | 2012-05-01 | Microcell Corporation | Fuel cell structures and assemblies with channeled current collectors, and method of making the same |
US6884539B2 (en) * | 2002-07-02 | 2005-04-26 | Microcell Corporation | Microcell electrochemical devices and assemblies with corrosion-resistant current collectors, and method of making the same |
US7473490B2 (en) * | 2002-07-02 | 2009-01-06 | Microcell Corporation | Fuel cell structures and assemblies with channeled current collectors, and method of making the same |
US7748101B2 (en) * | 2005-12-20 | 2010-07-06 | Ip Technologies Holdings, Llc | Method and apparatus for forming a metallic container |
US20070137020A1 (en) * | 2005-12-20 | 2007-06-21 | Ip Technologies Llc | Method and apparatus for forming a metallic container |
CN105789500A (zh) * | 2014-12-23 | 2016-07-20 | 比亚迪股份有限公司 | 电池的外壳及其制备方法以及电池、电池组、电池包和电动汽车 |
CN105789492A (zh) * | 2014-12-23 | 2016-07-20 | 比亚迪股份有限公司 | 电池的外壳及其制备方法以及电池、电池组和电动汽车 |
JP6276305B2 (ja) * | 2015-11-24 | 2018-02-07 | 有限会社中勢技研 | 溶融ナトリウム電池及び溶融ナトリウム電池用隔壁 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1038543A (fr) * | 1950-06-21 | 1953-09-29 | Philips Nv | Boîte métallique hermétique |
US3294591A (en) * | 1964-03-30 | 1966-12-27 | Gulton Ind Inc | Sealed battery |
US3306488A (en) * | 1965-12-27 | 1967-02-28 | Jerome H Lemelson | Container and liner therefor |
US3378406A (en) * | 1965-12-30 | 1968-04-16 | Leesona Corp | Metal-oxygen-containing electro-chemical battery |
GB1344565A (en) * | 1971-06-01 | 1974-01-23 | Gen Electric | Method of forming a metallic battery casing |
GB1392911A (en) * | 1972-09-09 | 1975-05-07 | Yuasa Battery Co Ltd | Storage battery |
JPS50153229A (fr) * | 1974-05-31 | 1975-12-10 | ||
CA1052859A (fr) * | 1975-03-17 | 1979-04-17 | Theodore R. Beatty | Pile alcaline plate munie de bornes collectrices positive et negative et d'une troisieme borne de connexion |
US4048393A (en) * | 1976-09-03 | 1977-09-13 | Ford Motor Company | Alkali metal battery structure |
US4127702A (en) * | 1977-10-11 | 1978-11-28 | Catanzarite Vincent Owen | Self-venting battery |
US4332868A (en) * | 1978-09-01 | 1982-06-01 | The Dow Chemical Company | High temperature battery cell comprising stress-free hollow fiber bundle |
DE3033130A1 (de) * | 1980-09-03 | 1982-04-01 | Brown, Boveri & Cie Ag, 6800 Mannheim | Elektrochemische speicherzelle |
DE3033438C2 (de) * | 1980-09-05 | 1986-08-21 | Brown, Boveri & Cie Ag, 6800 Mannheim | Elektrochemische Speicherzelle |
FI65688C (fi) * | 1981-04-27 | 1984-06-11 | Sporax Oy | Kontaktanordning foer battericell i ett galvaniskt batteri |
JPS61138473A (ja) * | 1984-12-07 | 1986-06-25 | Yuasa Battery Co Ltd | ナトリウム−硫黄電池とその製造法 |
DE8600472U1 (fr) * | 1986-01-10 | 1987-05-07 | Karl Huber Verpackungswerke Gmbh + Co, 7110 Oehringen, De | |
JPS6362165A (ja) * | 1986-09-01 | 1988-03-18 | Hitachi Ltd | ナトリウム−硫黄電池の製作法 |
-
1989
- 1989-07-25 GB GB898917022A patent/GB8917022D0/en active Pending
-
1990
- 1990-07-18 ZA ZA905639A patent/ZA905639B/xx unknown
- 1990-07-24 DE DE69018468T patent/DE69018468T2/de not_active Expired - Fee Related
- 1990-07-24 EP EP90910813A patent/EP0484368B1/fr not_active Expired - Lifetime
- 1990-07-24 CA CA002063802A patent/CA2063802A1/fr not_active Abandoned
- 1990-07-24 US US07/793,398 patent/US5279625A/en not_active Expired - Fee Related
- 1990-07-24 WO PCT/GB1990/001136 patent/WO1991001571A1/fr active IP Right Grant
- 1990-07-24 JP JP2510345A patent/JPH04507030A/ja active Pending
- 1990-07-24 AT AT90910813T patent/ATE120886T1/de active
- 1990-07-25 DD DD343072A patent/DD300890A5/de unknown
- 1990-07-25 CN CN90107250A patent/CN1049753A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
CA2063802A1 (fr) | 1991-01-26 |
ATE120886T1 (de) | 1995-04-15 |
US5279625A (en) | 1994-01-18 |
CN1049753A (zh) | 1991-03-06 |
DE69018468T2 (de) | 1995-07-27 |
DD300890A5 (de) | 1992-08-27 |
DE69018468D1 (de) | 1995-05-11 |
ZA905639B (en) | 1991-05-29 |
GB8917022D0 (en) | 1989-09-13 |
EP0484368A1 (fr) | 1992-05-13 |
JPH04507030A (ja) | 1992-12-03 |
WO1991001571A1 (fr) | 1991-02-07 |
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